Copolymer films of pyrrole and 3,4-ethylenedioxythiophene (EDOT) were synthesized electrochemically on the carbon fiber microelectrodes (CFME). Deposition conditions on the carbon fiber and influence of the monomer concentrations to the copolymerization as well as the electrochemistry of the resulting polymers and copolymers were studied using cyclic voltammetry, in-situ spectroelectrochemistry, FTIR-ATR and scanning electron microscopy. Effect of the monomer ratio on the formation of the copolymer was reported. The electroactivity and very well defined electrochemistry of both polymers polypyrrole and PEDOT, and copolymer of pyrrole and EDOT on the CFME as much as the Pt electrode pioneers the possibility of using these coated electrodes for bio-applications. A high level of stability to overoxidation has also been observed for PEDOT as the polymer on the CFME substrate show limited degredation of their electroactivity at potentials 1.2 V above its half-wave potential.